兩頭毛在云南作為一種彝族常用草藥,得到廣泛的臨床運(yùn)用,并具有較好抗炎療效,因此稱其為“肝炎草”,由于其在對抗炎癥方面效果顯著,而炎癥是通向腫瘤的一種渠道,考慮到炎癥和腫瘤的關(guān)系密切,本實(shí)驗(yàn)擬對兩頭毛的化學(xué)成分進(jìn)行系統(tǒng)研究,試圖尋找其有對抗腫瘤細(xì)胞靶點(diǎn)的活性化合物。本實(shí)驗(yàn)分離的化合物,對兩頭毛化學(xué)成分有進(jìn)一步認(rèn)識,對尋找具有抗腫瘤活性成分,提供一定的理論依據(jù),同時(shí)對兩頭毛的利用和開發(fā)具有重要的指導(dǎo)作用。

　　用三氯甲烷-甲醇(7∶3)洗脫,最后過硅膠柱,石油醚-乙酸乙酯(8∶1)洗脫,分別得到化合物3(25mg),化合物4(30mg)。Fr.4部分過MCI柱,用85%丙酮洗脫后,經(jīng)硅膠柱色譜,三氯甲烷-甲醇(20∶1,15∶1,10∶1,8∶1,6∶1)進(jìn)行梯度洗脫,得到Fr.4.1~Fr.4.4,共4個(gè)部分,Fr.4.3經(jīng)SephadexLH-20凝膠柱,以三氯甲烷-甲醇(5∶5)洗脫,得到化合物5(18mg)。3結(jié)構(gòu)鑒定化合物1白色粉末,mp222~224℃,ESI-MSm/z221[M+H]+。1H-NMR(500MHz,CDCl3)δH:5.05(1H,d,J=2.5Hz,H-6b),4.77(1H,d,J=2.5Hz,H-6a),4.28(1H,m,H-4),2.14(1H,dt,J=11.0,6.5Hz,H-3α),2.02(1H,m,H-9β),1.99(1H,m,H-8),1.95(1H,dt,J=11.0,7.0Hz,H-2),1.83(1H,m,H-3β),1.82(1H,d,J=14.0Hz,H-12β),1.78(1H,m,H-11),1.79(1H,d,J=14.0Hz,H-12α),1.61(1H,brd,H-10β),1.46(1H,dt,J=11.0,2.5Hz,H-10α),1.25(1H,m,H-9α),1.11(3H,s,H-14),1.19(3H,s,H-15),0.88(3H,d,J=7.0Hz);13C-NMR(125MHz,CDCl3)δC:162.7(C-5),104.3(C-6),77.3(C-4),58.5(C-1),55.6(C-12),49.3(C-11),46.1(C-2),39.1(C-13),39.0(C-3),38.3(C-8),35.1(C-15),28.2(C-10),26.9(C-14),26.3(C-9),17.6(C-7)。

　　上述NMR數(shù)據(jù)與文獻(xiàn)[4]報(bào)道一致,確證該化合物為suberosenolA。化合物2白色粉末,mp142~144℃,ESI-MSm/z221[M+H]+。1H-NMR(500MHz,CDCl3)δH:5.17(1H,s,H-6a),4.79(1H,s,H-6b),4.56(1H,d,5.5,H-4),2.39(1H,dd,J=11.5,7.5Hz,H-2),1.78(1H,ddd,J=13.5,7.5,4.0Hz,H-3α),2.08(1H,ddd,J=13.5Hz,7.0Hz,4.5Hz,H-3β),2.01(2H,m,H-8,9β),1.77(1H,m,H-11),1.66(1H,d,J=14.0Hz,H-12α),1.60(1H,m,H-10β),1.57(1H,d,J=14.0Hz,H-12β),1.48(1H,m,H-10α),1.28(1H,m,H-9α),1.15(3H,s,H-15),1.10(3H,s,H-14),0.96(3H,d,J=7.0Hz,H-7);13C-NMR(125MHz,CDCl3)δC:162.2(C-5),107.6(C-6),76.7(C-4),59.0(C-1),55.0(C-12),49.7(C-11),49.0(C-2),39.7(C-13),37.8(C-3),36.9(C-8),34.9(C-15),27.9(C-10),26.9(C-14),26.7(C-9),17.8(C-7)。

　　上述NMR數(shù)據(jù)與文獻(xiàn)[4]報(bào)道一致,確證該化合物為suberosenolB。化合物3無色油狀物,mp252~254℃,ESI-MSm/z219[M+H]+。1H-NMR(500MHz,CDCl3)δH:5.97(1H,d,J=0.75Hz,H-6a),4.98(1H,d,J=0.75Hz,H-6b),2.67(1H,dd,J=19.0,11.5Hz,H-3β),2.45(1H,dd,J=19.0,9.5Hz,H-3α),2.33(1H,t,J=11.5Hz,H-2),2.15(2H,m,H-8),2.08(1H,m,H-9β),1.88(1H,brs,H-11),1.80(1H,d,J=14.5Hz,H-12a),1.70(1H,d,J=14.5Hz,H-12b),1.71(1H,m,H-10β),1.60(1H,m,H-10α),1.35(1H,ddd,J=13.0,5.5,1.0Hz,H-9α),1.20(3H,s,H-15),1.17(3H,s,H-14),0.90(3H,d,J=7.0Hz,H-7);13C-NMR(125MHz,CDCl3)δC:208.5(C-4),151.8(C-5),115.3(C-6),57.8(C-1),54.3(C-12),49.8(C-11),45.2(C-2),41.8(C-3),40.2(C-13),36.5(C-8),35.0(C-15),27.8(C-10),27.0(C-14),26.5(C-9),17.4(C-7)。上述NMR數(shù)據(jù)與文獻(xiàn)[5]報(bào)道一致,確證該化合物為suberosenone。化合物4黃色針晶,mp237~239℃,ESI-MSm/z433[M+H]+.1H-NMR(500MHz,DMSO-d6)δH:1.14(3H,d,J=6.5Hz,CH3-5″),3.3~3.5(2H,m,H-3″,4″),3.66(1H,d,J=8.5Hz,H-2″),3.85(1H,brs,H-5″),5.56(1H,d,J=1.1Hz,H-1″),6.41(1H,d,J=2.0Hz,H-6),6.82(1H,d,J=2.0Hz,H-8),6.93(2H,d,J=8.5Hz,H-3',5'),8.09(2H,d,J=8.5,H-2',6');13C-NMR(125MHz,DMSO-d6)δC:17.7(C-6″),69.7(C-5″),69.9(C-2″),69.9(C-3″),71.5(C-4″),94.4(C-8),98.3(C-1″),98.7(C-6),115.5(C-3',5'),121.5(C-1'),129.6(C-2',6'),155.5(C-9),159.2(C-4'),160.4(C-5),161.3(C-7),176.1(C-4)。上述NMR數(shù)據(jù)與文獻(xiàn)[6]報(bào)道一致,確證該化合物為山奈酚-7-O-α-L-鼠李糖苷。化合物5淡黃色針狀結(jié)晶(甲醇),mp171~172℃。1H-NMR(500MHz,MeOD)δH:7.58(1H,d,J=2.0Hz,H-2),7.15(1H,d,J=8.0Hz,H-5),7.04(1H,dd,J=8.0,2.0Hz,H-6),6.78(1H,d,J=15.8Hz,H-7),6.30(1H,d,J=15.8Hz,H-8),3.88(3H,s,-OCH3);13C-NMR(125MHz,MeOD)δC:128.0(C-1),112.0(C-2),150.8(C-3),149.6(C-4),116.2(C-5),116.8(C-6),147.2(C-7),124.4(C-8),171.3(C-9),56.7(-OCH3)。以上數(shù)據(jù)與文獻(xiàn)[7]報(bào)道的阿魏酸的基本一致。